Synthesis of poly(2‐methoxyethyl acrylate) by single electron transfer—Degenerative transfer living radical polymerization catalyzed by Na₂S₂O₄ in water

Abstract

Living radical polymerization of 2-methoxyethyl acrylate (MEA) was achieved by single-electron-transfer/degenerative transfer mediated living radical polymerization (SET-DTLRP) in water catalyzed by sodium dithionate. The poly(2methoxyethyl acrylate) is an amphiphilic polymer with a hydrophobic part (polyethylene chain) and a mildly hydrophilic tail. The plots of number-average molecular weight versus conversion and ln{[M] 0 /[M]} versus time are linear, indicating a controlled polymerization. This method leads to the preparation of a,x-di(iodo) poly(2methoxyethyl acrylate)s (a,x-di(iodo)PMEA) macroinitiators that can be further functionalized. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right-angle light scattering (RALLS), a differential viscometer (DV) and refractive index (RI). The method studied in this work represents a possible route to prepare well-tailored macromolecules made of 2-methoxyethyl acrylate (biocompatible material) in an environmentally friendly reaction medium. To the best of our knowledge there is no previous report dealing with the synthesis of PMEA by any LRP approach in aqueous medium.

Synthesis and Reactivity of Mononuclear Iron Models of [Fe]‐Hydrogenase that Contain an Acylmethylpyridinol Ligand

“…A typical proton NMR spectrum of a PMA‐Br is demonstrated in Figure 8. The assignment of proton resonances has been done according to references: ( e, g, f, f' ),3, 8, 29 ( a, b, c ),3, 30 ( d r , d m ) 3, 31–34. The signal of the initiator methyl a is overlapped with the signal of paraffin grease trace at δ = 1.263, 35 and the signal of protons d r is partially overlapped with the signal of water trace in CDCl 3 at δ = 1.6 3, 35.…”

“…There are also traces of THF (resonances at δ = 1.85 and 3.76),35 which was used for PMA purification. The fractions of syndiotactic and isotactic diads ( d r and d m respectively) were obtained by measuring the integrals of signals d m and d r 31–34. The percentage of the chain‐end functionality was calculated as follows: percentage functionality = [ I ( g )/( I ( c )/6)] × 100%; where I ( g ) is the integral of the PMA terminal bromo chain‐end –CH 2 –C H g Br(CO 2 Me) at δ = 4.25 and I ( c ) is the integral of the initiator fragment –CH(C H c 3 ) 2 CO 2 Et at δ = 1.1 3.…”

Polymeric bile acid sequestrants—Synthesis using conventional methods and new approaches based on “controlled”/living radical polymerization

“…Polymers that can be used as common BAS backbones (see Sections 3.1 and 3.2) have already been synthesized by CLRP techniques. These include amine/ammonium functionalized poly(styrene)s [103,104], poly(meth)acrylamides [105,106], poly(meth) acrylates [107][108][109][110] and polyethers. Polymer structures options include homopolymers and copolymers with complex architectures and controlled molecular weight.…”

Synthesis of Graft Copolymers Based on Poly(2‐Methoxyethyl Acrylate) and Investigation of the Associated Water Structure

“…[ 5 ] Our group has carried out exhaustive investigations covering polymerization kinetics of copper (I)-catalyzed ATRP of MEA as well as end-group analysis and chain extension reaction to obtain block copolymers of PMEA while probing different catalytic complexes, reaction milieu, and temperature. [ 6 ] Coelho et al [ 7 ] obtained PMEA by single electron transfer-degenerative transfer radical polymerization; however, the molecular weight distributions (MWD) were rather broad. PMEA and random copolymers of MEA with 2-hydroxyethyl acrylate were prepared by RAFT and nitroxide-mediated homo-and copolymerization, respectively, and the thermoresponsive properties of these materials were assessed.…”

“…The molecular weight and the MWD were obtained by SEC employing the light scattering detector (dn/dc = 0.060). [ 7 ] P(Br P(Br i BuEMA 9 -co -MEA 23 ) (49 mg, 0.075 mmol of the initiating sites), MEA (5 mL, 38.9 mmol), CuBr (17 mg, 0.12 mmol), PMDETA (25 μ L, 0.12 mmol), DMF (5 mL), and anisole (5 mL) were taken. The polymerization was allowed chromatography (SEC) using the following instrument: Viscotek GPCmax VE-2001 equipped with Viscotek TriSEC Model 302 triple detector array (refractive index detector, viscometer detector, and laser light scattering detector with the light wavelength of 670 nm, and measuring angles of 90 ° and 7 ° ) and a Knauer K-2501 UV detector using two PLgel mixed-D columns from Polymer Laboratories (PL).…”